Process of manufacturing hydrocarbons and cyanides



Monmouth and State which,

- UNITED stares PATENT orrice.

JOHN COLLINS CLANCY, 0F ASBURY PARK, NEW JERSEY.

PROCESS OF MANUFACTURING HYDROGARBON S AN D CYANIDES.

To all. whom it may 0on0 Be itknown that I,

em: JOHN CoLLINs CLANoY, citizen of the United States, and

resident of ,Asbury Park 1nvented certain new ydrocarbons and Cyanides, of which thefollovving is a specificatio in the count of This invention relates to the manufacture of hydrocarbons and cyanide; and itcomprises a method of destructively, distilling l carbonaceous material While the latter solid is immersed in a fused cyanide reagent, and

in th or combination therewith mg" process,

tilling lation of a cyanide makthrough' the intermediacy of the cyanide decomposed in the dis step is reconstituted from the distilresidues, and the recovery of the cyanide content from the latter automatically effected by utilizing sai manufacture of additional cyanide.

d residues in the carbonaceous material may be in the nature of carbohydrates, sawdust bitumen,

lignite, and in particular,

The object of this inve from the aforesaid mat coal, higher percentages carbons than are hitherto practised tional cyanide that the cost, not cyanide recovery step, but also -coal.

ntion is to recover erial, particularly of liquidhydroobtained by any of the processes of destructive distillation, and to reclai m the cyanide reonly of the that of the distilling operation is thereby very much reduced in that it enables t nation of non-coking or coals or other solid fuels he profitableutilipoorly coking eretofore not successfully treated by destructive distillation processes.

In my pending Process of application entitled:

cracking oils Serial filed Septeimber 2, 1922 I h No. 586,029; .ave disclosed the -;en' cyanide in the treatment of uch as shale and of hydrocarbons the process as described in said application, I separated the coky residuum or finely divided carbon from the molten cyanide conta reaction products by filtr ined in the fusion ation of the latter these results,

Application filed April .18, 1925. Serial No. 24,270.

method on'the fusion residues resulting from the treatment of coal with molten cyanide, however, a difficult carbonaceous residuum at a red heat, as much as to of the cyanide is still trapped in the cokyresiduum. Obviously of course this ma be recovered from the cohy mass by su1table leaching, but any sur h procedure obviously involves considerable expense, imposed upon a process already burdened by the low market value of some or all of its reaction products.

have therefore sought and have found such a combination of steps as will not only from coal as disclosed in mysaid co-pending case; but which will further afford an etiicient recovery of said cyanide, moreover, While satisfactorily accomplishing I have succeeded in going still further, in that my present process not alone affords liberation of the cyanide trapped in the coky mass, but actually gives more than one hundred percent of cyanide yield therefrom.

In brief, I do not remove the cyanide mass but rather I remove the mass from the cyanide by fixing the carboi thereof in the form of additional cyain e.

According to my invention, carbonaceous material either in the form of sawdust, carbohydrates, bitumen, peat, lignite, or cal, and particularly the latter, is reduced to a finely divided state and admixed with a suitable hydrocarbon oil, such as petroleum, shale oil, heavy tar oil, or the like, to form an emulsion or suitable mixture. This mixture, advantageously in a preheated condition, is then conimingled with molten cyanide reagent and distilled under carbonizing temperatures and under pressure which can be regulated so as to produce from the about sixty pounds per square ammonia which in coal, a large proportion of hydrocarbon oils. The moisture content of the coal rcacts with the molten cyanide to produce part decomposes and tends to h drogenate the coal to produce lar er y'iel s of saturated hydrocarbons.

ther side reactions take place between the decomposition products of the cyanide and the coal, to form free hydrogen an carbon monoxide, the latter reaction tending to further hydrogenate the coal. Dry ammonia gas, may be advantageously bubbled through the molten mixture during the latter part of the i to assist in the agitation of the fusion products; and which gas, towards the end of the distilling operation, reacts with the cyanide decomposition products in the presenceo carbon to promote a cyanide forming reaction. Permanent hydrocarbon gases, suc as still gases, may be advantageously use in conjunction with furthe'r assist in said agitation. 'The evolved hydrocarbon vapors and gases are suitably collected.

The fusion residues left in the still, comprisin carbonaceousresiduum, alkali metal cyani e are discharged from the still preferably as a free flowing moltenmagma which is thereafter treated to reconstitute the cyanide decomposed by the moisture content of the coal, and to recover the cyanide from said magma and also to utilize the latter in the manufacture of additional cyanide in the manner hereinafter described. I

In carrying my process into practice,

first charge molten cyanide reagent Into a.

closed vessel or-still made of any suitable material, such as iron. continueduntil the still is about half filled with said cyanide. The cyanide used may be sodium cyanide of commercial urity, with a melting point around 500 the low melting point of the latter compound being due to im urities such as sodium sulpho-cyanide, an other alkalinous metal compounds. The cyanide is maintained in the molten condition withinthe still by the application of heat thereto. The mixture of coal and oil, prepared as described in the foregoing paragraph, is slowly introduced at a low point in the still so that itenters'well below the surface of the bath of molten cyanide. As the oil-coal mixture-is fed in, the pressure inside the still rises while the coal is commingled by the agitation of bubbling of the oil vapors through the depth or bath of the molten cyanide. The pressure is regulated according to the temperature desired in the still. A convenient pressure is inch, but this pressure may be varied up or down during the introduction of the coal. As vapors from the oil first pass off into the vapor distilling operation,

h 700 0.; the vapors d tilling operation being suitably collected the ammonia gas to.

and its decomposition products,-

' The charging a is -rgsasea coal oil mixture, the pressure thereby imposed upon the coal (especially if the coal is of the bituminous variety) causes the latter to first melt and become more or less miscible with the molten cyanide thereby presenting an extensive surface to thecyture; namely, a proportion of coalapproximately equal to about half the weight of the volume of the molten cyanide used, lgradually release the pressure and carry on the distillation of the volatile matter either under atmospheric pressure or in a vacuum, but preferably around atmospheric pressure. During the latter operation I prefer to gradually increase the temperature of the molten body in the still up to say around evolved during the disand condensed.

A convenient form of still is a cylinder or a tube with an agitator or with a worm or spiral agitator moving the mixture forward to the discharge end but any ordinary still of suitable material'such as iron may also be used with or without an agitator.

After the completion of distillation, the carbonaceous residuum or finely-divided coke left in the still, remains largely in suspension in the molten cyanide mixed with its decomposition products. To insure suspension of the coky residuum in the molten bath I continue the bubbling of still gases therethrough until the molten magma is ready for discharging. If insuflicient cyanide has been used, the residual products give rise to a sticky molten magma which is difficult to discharge from the still and requires the addition of a further quantity of molten cyanide to facilitate its discharge therefrom. It is advisible to add at the start, sufficient cyanide to prevent the formation of such sticky fusion residues.

We are now confronted with the problem of the recovery of the cyanide. Filtration or liquation of a portion of the cyanide from the fusion residues might be resorted to; rovided that such fusion residues ha not een allowed to become too concentrated in coky residuum. However, as such an op-.

space of the still during the charging of the .anide for reaction therewith. After the still d has received its quota of coal and oil mixoration does not reconstitute tho cyanide docomposed by the moisture content of the coal, nor, does it recover the cyanide absorbed or trapped in the coky niass,-it is preferable not to undertake such filtration o1 liquation, in view of my discovery of the feasibility of so treating these coky residues aslo, in effect separate these coky residues themselves from therein, rather than to remove the said cyanide fromthe said residues. In other Words, I have found it to be the much more economical course, to remove the trap-conthe cyanide entrapped carb stituting residuum bodily, so to speak, from the entrapped substance, in contradlstinction to any attempt to remove the latter from the former.

I have made the discovery residuum in question admixed as it is, with cyanide and with the decomposition products of cyanide,is peculiarly Well adapted to participate in a reaction with alkalinous metal carbonate, such as sodium carbonate,

that the coky and nitrogen or a nitrogenous gas to not alone reconstitute the decomposed cyanide, but to further form additional cyanide, the on of the residues being the source of the carbon content of such additional cyanide. I a

This reaction is effected at a cyanide forming ten'iperature, the carbonate being admixed with the still molten and hence highly heated residues aforesaid, and the nitrogen or its equivalent, being bubbled up through the molten mass, in a suitable furnace, such as is ordinarily used for making cyanide by the Bielby or Castner processes.

Thus, the very substance which would ordinarily be regarded as a source of trouble and expense, and from which the trapped cyanide could normally be separated this trapped cyanide by being itself comlined with other substances to form an additional and auxiliary quantity of the substance being freed, to wit,cyanide.

The molten cyanide produced in the foregoing manner is usually contaminated with more or less finely. divided carbon, this carbon.'however, is readily separated by simple filtration from the cyanide while the latter is in themolten state. The residue of carbon after filtration still contains more or less absorbed cyanide. This residue may be treated with steam to produce ammonia from its cyanide content, by this well known method of cyanide hydrolysis. I have discovered that the ammonia so produced, after being dried, may be used, advantageously, in admixture with nitrogen in the cyanide forming step, I have found that even as small an addition as 2% by volume of am monia in admixture with nitrogen or in admixture with a carbonaceous gas containing nitrogen. greatly facilitates the fixation of nitrogen in the said cyanide forming step and that the temperature and time of such reduced by its use.

reaction can be materially The 'arbon residue from the aforesaid steamingoperation may be leached with water to remove soluble salts and yield sulphur and ash free carbon, in other words, substantially pure 'arbon, the latter having a relatively high market value.

It is obvious that the cyanide reclaimed and manufactured in the cyanide forming step of the described process may contain as rm purities, small quantities of other alkalinous metal cyanides besides sodium cyanide, such cyanides, the base of which correspond to some of the alkalinous ash constituents of the carbonaceous material. For example, if sawdust be the carbonaceous material treated, some potassium cyanide will be, formed in proportion to the potash content of this material. On the other hand. when treating coal, alkalinous cyanides and sulpho-cyanides of the alkali ash and sulphur content thereof will be formed. The aforesaid impurities however, do not accumulate, for the reason that, any portion of the cyanide reused in the process for treating additional quantities of carbonaceous material, is thereafter admixed with the fresh sodium cyanide produced through the intermediacy of the aforesaid cyanide forming step. By this means the percentage of impurities are kept more or less constant.

wing to the presence of sodium sulphocyanide and other impurities referred to; any portion of the canide reagent used for treating additional quantities of coal will have a lower melting point than if pure sodium cyanide were used as a cyanide reagent or starting material. The low melting point of the cyanide reagent is especially advantageous in the treatment of bituminous coal, in that, when the latter is brought into contact with a cyanide reagent of low melting point, it commingles therewith without perceptible intumescence; this together with the property possessed by molten sodium cyanide of holding considerable quantities of finely divided coal or other carbonaceous material in suspension allows of its use in the treatment of a very large variety of solid fuels.

\Vhile l have described the method of destructively distilling comminuted carbonaceous material by admixing the latter with a suitable liquid hydrocarbon and then bringing this mixture into contact with molten cyanide, it must be understood, however, that the finely divided carbonaceous material. such for example as coal, may be introduced into the still without such ad; mixture with liquid hydrocarbon. For example, finely divided coal may be delivered into contact with the molten cyanide by means of a suitable screw conveyer or other mechanical means. The preferred method, however, is to form a mixture of the finely divided coal with a suitable hydrocarbon liquid as described. The presence of the liquid hydrocarbon. such for example as a heavy oil acts to more or less soften the coal and functions as a kind of regulator of the destructive distillation of the coal while at the same time acts as a carrier for introducing the coal into contact with the molten cyanide. y

The hydrocarbon oil so added or mixed with the coal will also distill over to a large iii extent. and be recovered with the hydrocarbon oils from the coal, but the principal function of the hydrocarbon oil is to facilitate as aforesaid the deliver of the coal to the molten cyanide in the sti l.

, It is obvious that, instead of bringing the carbonaceous material into contact with the molten cyanide .by the methods described; the carbonaceous material, for example, finely divided coal may be mixed with solid cyanide in the subdivided form and this mixture charged into the still and brought up to a destructive distillation temperature whereby the cyanide melts and reacts with the coal to produce hydrocarbons and other volatile reaction products, time supplying the fusion coky residuum for the cyanide forming step. Using this method, however, much of the moisture is driven off from the coal before it has the opportunity of reacting with the cyanide in the molten state to establish hydrogenating reactions as hereinbefore referred to. The preferred method is to the molten state as described. The molten cyanide reagent used in the process maybe obtained, after the process has been in operation, from any portion of themolten cyanide produced in the cyanide forming step of the process, thereby saving the expense and time required in heating solid cyanide to the melting pointor to a molten state.

As indicated, sodium carbonate is the pre ferred alkali-base-supplying agent employe in the cyanide forming step of the process principally because it gives satisfactory results and is inexpensive. Instead of sodium carbonate I may employ other sodium salts, such as sodium hydroxide, sodium bi-carhouate or sodium salts of similar organic acids. Sodium carbonate, however is the logical alkali metal compound for use in the cyanide forming step of my process, and the distillation fusion residues are preferably admixed with the said carbonate while the latter is in the molten state to facilitate uniform mixture of the reactants.

What I claim is:

1. The method of manufacturing hydrocarbons and cyanides which comprises, destructively. distilling solid carbonaceous material while the latter is immersed in a molten alkali metal cyanide reagent, collecting the volatile reaction products, reconstituting the cyanide decomposed in the distilling step andJiberating cyanide trappe in the dist llation residues, by subjecting the latter to a cyanideforming reaction in Whic participate Sllfl'lC'lBIlt alkali and nitrogen to combine w h part at least of the carbon content of said residues to form additional alkah metal cyanlde, thereby reclaiming cyanide reagent in admixture with the additional cyanide produced through the inter-' while at the same use the cyanide in.

d and to h distillation residues,

mediacy of the said cyanide forming reaction.

2. The process of manufacturing hydrocarbons and cyanides which comprises, subjecting to distillation a mixture of comminuted carbonaceous material, a heavy hydrocarbon oil and molten sodium cyanide, under suitable pressure and temperature, to produce hydrocarbons which are liquid at normaltemperature and pressure, and a fusion residue containing mixing the said fusion residue with sodium carbonate, subjecting the so formed mixture to the action of a nitrogenous gas under alkali metal cyanideforming conditions to fix part at least of the carbon content of the said fusion residue in the form of additional sodium cyanide and to reconstitute the cyanide decomposed in the distilling step, thereby reclaiming the originally used quantity of sodium cyanide in admixture with the additional cyanide cyanide forming conditions.

3. The process of manufacturing hydro-- carbons and cyanides which comprises, distilling a mi 'ture of finely divided coal and a hydrocarbon oil in admixture with molten sodium cyanide reagent under suitable ressure and temperature, to produce hydr carbons which are liquid at normal pressure and temperature, releasing the pressure and increasing the temperature towards the end of the distilling o eration to; drive ofi heavier volatile and hquefiable hydrocarbons obtain a fusion residueeontaining coky residuum, mixing the said fusion residue with sodium carbonate, subjecting the so formed mixture to the action of a nitrogenous gas under alkali metal cyanide forming conditions to fix part at least of the carbon content of said fusion residue in the form of additional sodium cyanide and to reconstitute the cyanide decomposed in the distilling step, thereby reclaiming sodium cyanide reagent in admixture with the additional sodium cyanide produced under said cyanide forming conditions.

4. The process of manufacturing hydrocarbons and alkali metal cyanides which comprises, destructively distilling finely divided coal while the latter is immersed in a molten sodium cyanide reagentunder suitable pressure and temperature to produce liquid hydrocarbons and fusion residue containing coky residuum, reconstituting the ayanide decomposed by themoisture content 1 of the coal and simultaneously liberating part at least of the cyanide trapped in the by subjecting the latter to a cyanide forming reaction in whichparticipate sufficient sodium carbonate and coky residuum,

produced under said nitrogen to combine with a portion of the 1 carbon content at least, the so liberated cyanide for treating additional quantities of coal.

thereof, and reusing, in part 5. The

process of manufacturing hydrostructively distilling a mixture vided coal ture with finely diand a hydrocarbon oil in admixproduce liquid hydrocarbons and other volaresiduum,-

volatlle reactlon products, mlxmg the afore-,

tile reaction products, releasing the pressure and increas ng the temperature towards the end of the distilling operation to drive off heavier volatile hydrocarbons and to obtain a molten fusion residue containing coky collecting such hydrocarbons and said molten fusion sodium carbonate,

residue with molten suiqectmg the so formed to fix part at least of the carbon content of the said fusion residue in the form of additional sodium cyanide and to reconstitute the cyanide decomposed in the distilling step, thereby reclaiming the cyanide admixture with the additional cyanide produce under said cyanide forming conditions reagent into a cyanide forming reaction in which participate sufiicient alkali and nitrogen to reconstitute the cyanide decomposed in the distilling step and to form additional cyanide through chemical combination with a portion at least of the carbon content of said residues.

7. The process of manufacturing hydrocarbons and cyanides which'comprises, de-' structively distilling comminuted carbonaceous material in contact with molten a1- kali metal cyanide, collecting the volatile reaction products, and subjecting the distillation rcsdue's to a cyanide forming reaction to reconsl itute the cyanide decomposed in the disltilling step and to form additional cyamc e.

8. The process of manufacturing hydrocarbons and cyanides which comprises, destructively distilling a mixture of finely divided carbonaceous material and a hydrocarbon oil in contact with molten alkali metal cyanide, collecting the volatile reaction products, and Sub ecting the distillation residues to a cyanide forming reaction to reconstitute the cyanide decomposed in the distilling step andto form additional cyanide.

In testimony whereof, I aflix my signature hereto.

JOHN COLLINS onANoY. 

